Crystalline CO 2 ‐Based Aliphatic Polycarbonates with Long Alkyl Chains

Carbon dioxide (CO 2 ) is an easily available, renewable carbon source and can be utilized as a comonomer in the catalytic ring‐opening polymerization of epoxides to generate aliphatic polycarbonates. Dodecyl glycidyl ether (DDGE) is copolymerized with CO 2 and propylene oxide (PO) to obtain aliphatic poly(dodecyl glycidyl ether carbonate) and poly(propylene carbonate‐ co ‐dodecyl glycidyl ether carbonate) copolymers, respectively. The polymerization proceeds at 30  ° C and high CO 2 pressure utilizing the established binary catalytic system ( R,R )‐Co(salen)Cl/[PPN]Cl. The copolymers with varying DDGE:PO ratios are characterized via NMR, FT‐IR spectroscopy, and SEC, exhibiting high molecular weights between 11 400 and 37 900 g mol −1 with dispersities ( Ð  =  M w / M n ) in the range of 1.37–1.61. Copolymers with T g s of −11  ° C or T m s from 5 to 15  ° C and thermal decomposition >200  ° C depending on the comonomer ratio, are obtained as determined by differential scanning calorimetry/TGA.